Cyclic oxime derivatives

ABSTRACT

Cyclic oxime derivatives of the isomeric formulae   WHEREIN R1, R2, R3 and R4 have the respective meanings set out in the specification following, these derivatives being useful as herbicides.

United States Patent [191 Kirby et al.

CYCLIC OXIME DERIVATIVES Inventors: Peter Kirby, Maidstone; Eirlys R.

Isaac, Stittingbourne; Graham C. Smith, Ramsgate, all of EnglandAssignee: Shell Oil Company, Houston, Tex.

Primary Examiner-Henry R. Jiles Assistant Examiner-Robert T. Bond Filed:Nov. 24, 1972 Appl. No.: 309,566 [571 ABSTRACT Cyclic oxime derivativesof the isomeric formulae CHgO R CH 0 2 n -c-o A-g-R R C}0R c\ "-11 A ffR3 ca on CH 0 N-R Foreign Application Priority Data wherein R R R and Rhave the respective mean- Nov. 29, 1971 United Kingdom .2 55319/71 ingsSet out in the Specification following, these derivatives being usefulas herbicides. US. Cl. 260/340.7; 260/340.9; 424/278;

71/88 1m. 0.. C07d 15/04; C07d 13/08; C07d 13/02 7 N Drawmgs Field ofSearch 260/340.7, 340.9

[ June 3, 1975 CYCLIC OXIME DERIVATIVES DESCRIPTION OF THE PRIOR ART Asearch of the prior 'art has indicated that the herbicidal oximederiatives of this invention are novel.

DESCRIPTION OF THE INVENTION The present invention relates to cyclicoxime derivat1ves having one or the other of the following isomericformulae:

sents an alkyl group of 1-6 carbon atoms, for example methyl; Rrepresents an alkyl or alkoxycarbonyl group of up to 6 carbon atoms, forexample methyl or ethoxycarbonyl, or a phenyl group; R represents ahydroxy group; R represents a benzyl group; and A represents a covalentbond.

The following compounds are particularly preferred:2-acetyl-4-benzyloxymethyl-2,4-dimethyl-1,3-

dioxolane oxime, 2-acetyl-4-benzyloxymethyl-2,4-dimethyl-l ,3-

wherein R and R each represents an alkyl group; R3 represents a hydrogenatom or an alkyl, acyl or phenyl group, or R and R together represent apolymethylene p; 4 represents a hydroxy group or an alkali metal saltthereof, an alkoxy group optionally substituted by a cyano, alkoxy oracyl group, an alkynyloxy group an acyloxy group, a benzyloxy group, oran amino group substituted by one or two alkyl groups or by an acyl 01'dimtrophenyl group; R represents a benzyl group ptionally substituted byone or more halogen atoms or by an alkyl group; and A represents acovalent bond or a methylene group. The term acyl is used herein in itsbroadest sense to denote a group formed by the removal of a hydroxy]group from an organic acid, and includes therefore not only groupsderived from carboxylic or thiocarboxylic acids, such as alkanoyl or0ptionany N-substituted carbamoyl or thiocarbamoyl p but also groupsderived from substituted carbomc acids, such as alkoxycarbonyl groups.

Preferred carbonyl derivatives are those compou of formula I wherein Rand R each represents an alkyl group of 1-6 carbon atoms, for examplemethyl Or ethyl; R represents a hydrogen'atorn, an alkyl oralkoxycarbonyl group of up to 6 carbon atoms, for example methyl orethoxycarbonyl, or a phenyl group, OI 2 and R together represent apolymethylene gr p Of'uP to carbon atoms, for example trimethylene; 4 psents a hydroxy group or a sodium salt thereof, an alkoxy group of l6carbon atoms, forexample methoXy, optionally substituted by a cyanogroup, by a alkoxy or alkoxycarbonyl group of upto 6 carbon atoms, forexample by methoxy or methoxycarbonyl, or by an phenylcarbamoyl group,an alkynyloxy or alkahoyl xy group of up to 6 carbon atoms, for examp PPY Y" or y. a carbamoyloxy, group mono-N- substituted by an alkyl oralkenyl group of up to 6 carn atoms, for example by methyhethyl orpropenyl,

I y a p yl group, for example by dichloro- P y a benzyloxy group, or anamino group substituted by two alkyl groups-each of 1-6 carbon atoms,for example methyl or by a thiocarbamoyl, benzoyl or dinitrophenylgroup; R represents a benzyl group op i ally substituted by two chlorineatoms or by an alkyl group of 1-6 carbon atoms, for example by methyl; nA represents a covalent bond or a methylene group,

compounds of formula II wherein R and R each repredioxolaneO-methyloxime, and 2-acetyl-4-benzyloxymethyl-4-ethyl-2-methyll ,3-

dioxolane oxime It will be appreciated that the carbonyl derivatives ofthe invention may exhibit geometrical and optical isomerism. Theindividual isomers together with mixtures thereof are included withinthe scope of the invention.

The compounds wherein R represents a hydroxy group or substituted aminogroup are prepared by a process which comprises reacting a diol offormula:

in the presence of an acid catalyst, for example ptoluene sulphonicacid. The reaction is preferably carried out in an aromatic hydrocarbon,for example benzene, as solvent.

Those compounds wherein R represents an optionally substituted alkoxygroup or an alkynyloxy, acyloxy or benzyloxy group are obtained byreacting the corresponding compound wherein R represents a hydroxy groupwith a strong base, forexample an alkali metal, hydride such as sodiumhydride, and a halo compound kali metal salt formed in the first stageof the process may be isolated from the reaction mixture.

When R represents a mono-N- substituted carbamoyloxy group the compoundsmay alternatively be prepared by reacting the corresponding compoundwherein R represents a hydroxy group with an isocyanate, suitably in thepresence of a tertiary amine such as triethylamine.

As mentioned above the carbonyl derivatives of the invention are ofinterest as herbicides, and in particular as herbicides for thepre-emergence control of grass weeds. The invention includes thereforeherbicidal compositions comprising carrier or a surface-active agent, orboth a carrier and a surface-active agent, together with, as activeingredient, at least one compound of the invention. Likewise theinvention includes also a method of combating undesired plant growth ata locus which comprises applying to the locus a herbicidally effectiveamount of a compound or composition of the invention.

The term carrier as used herein means a solid or fluid material, whichmay be inorganic or organic and of synthetic or natural origin, withwhich the active compound is mixed or formulated to facilitate itsapplication to the plant, seed, soil or other object to be treated, orits storage, transport or handling.

The surface-active agent may be an emulsifying agent or a dispersingagent or a wetting agent; it may be nonionic or ionic.

Any of the carrier materials or surface-active agents usually applied informulating pesticides may be used in the compositions of the invention,and suitable examples of these are to be found, for example, in ourBritish Specification No. 1,232,930.

The compositions of the invention may be formulated as wettable powders,dusts, granules, solutions, emulsifiable concentrates, emulsions,suspension concentrates and aerosols. Wettable powders are usuallycompounded to contain 25, 50 or 75% w of toxicant and usually contain,in addition to solid carrier, 3l0% w of a dispersing agent and, wherenecessary, -l0% w of stabiliser(s) and/or other additives such aspenetrants or stickers. Dusts are usually formulated as a dustconcentrate having a similar composition to that of a wettable powderbut without a dispersant, and are diluted in the field with furthersolid carrier to give a composition usually containing /2-l0% w oftoxicant. Granules are usually prepared to have a size between and 100BS mesh (1.676 0.152 mm), and may be manufactured by agglomeration orimpregnation techniques. Generally, granules will contain /2-25% wtoxicant and 0-10% w of additives such as stabilisers, slow releasemodifiers and binding agents. Emulsifiable concentrates usually contain,in addition to the solvent and, when necessary, co-solvent, l050% w/vtoxicant, 2-20% w/v emulsifiers and O-% w/v of appropriate additivessuch as stabilisers, penetrants and corrosion inhibitors. Suspensionconcentrates are compounded so as to obtain a stable, non-sedimenting,flowable product and usually contain 10-75% w toxicant, 0.5 15% w ofdispersing agents, 0.1 10% w of suspending agents such as protectivecolloids and thixotropic agents, 0 10% w of appropriate additives suchas defoamers, corrosion inhibitors, stabilisers, penetrants andstickers, and as carrier, water or an organic liquid in which thetoxicant is substantially insoluble; certain organic solids or inorganicsalts may be dissolved in the carrier to assist in preventingsedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions obtained bydiluting a wettable powder or a concentrate according to the inventionwith water, also lie within the scope of the present invention. The saidemulsions may be of the water-in-oil or of the oilin-water type, and mayhave a thick mayonnaise-like consistency.

The composition of the invention may also contain other ingredients, forexample, other compounds possessing pesticidal, especially insecticidal,acaricidal, herbicidal and fungicidal properties.

The invention is further illustrated in the following examples.

EXAMPLE 1 2-Acetyl-4-benzyloxymethyl 2,4-dimethyl 1,3-dioxolane oxime(isomers A and B) 3-Benzyloxy 2 methylpropane 1,2 diol (20 g), butane2,3 dione monoxime (10 g) and p toluenesulphonic acid (0.2 g) in benzene(50 ml) were heated together at reflux temperature under a Dean andStark trap for 16 hours. When a total of 0.8 ml of water had beencollected in the trap the solvent was removed from the reaction mixtureand the residue was chromatographed on silica gel using a 4:1 mixture ofmethylene chloride and ether. The product so obtained was shown by IRand NMR spectroscopy to be an isomer mixture. On repeatedrecrystallisation of this mixture from petroleum ether (b.p. 6080C) pureisomer A was obtained (m.p.8384C).

Analysis Calculated for C H NO C 64.5 H 7.6 N 5.0 I Found :C64.7'H7.4:N5.l

The mother liquors from the recrystallisation-of the isomer mixture wereevaporated to dryness under reduced pressure and the residue wasrecrystallised from petroleum ether to give a product containing ca.75%isomer B and 25% isomer A (as shown by NMR spectroscopy). Isomer B ischaracterised by an absorption band at 3380 cm in its IR spectrum.

EXAMPLE 2 2 Acetyl 4 benzyloxymethyl 4 ethyl 2 methyl 1,3 dioxolaneO-(N-ethylcarbamoyl) oxime' 2-Acetyl 4 benzyloxymethyl 4- ethyl 2 methyl1,3 dioxolane oxime (0.6 g, prepared by a similar method to that ofexample 1) in methylene chloride (25 ml) was treated withethylisocyanate (0.2 g) and triethylamine (2 drops). The solvent wasthen removed under reduced pressure and the residue was taken upinpetroleum ether. The solution was decanted from the undissolvedtriethylamine and evaporated to yield the desired product.

Analysis Calculated for CygHggNgOgg Found EXAMPLE 3 dioxolane 0proparglyoxime 2 Acetyl 4 benzyloxymethyl 2,4 dimethyl 1,3 dioxolaneoxime 91.49 g, /50 isomer mixture prepared as in example 1) wasconverted to its sodium salt by reaction with sodium hydride (0.12 g) indimethylformamide (20 ml). Propargyl bromide (0.6 g) was added to thesolution of the salt and the mixture was allowed to stand for 16 hoursat room temperature. It was then poured into water and extracted withether. The ethereal extracts were dried and the ether was removed underreduced pressure. The residue was purified by chromatography on silicagel using methylene chloride followed by 4:1 methylene chloride/ethermixture as eluant to yield the desired product.

ples l 3 further compounds were prepared, whose physical characteristicsand analyses are set out in Table 1.

EXAMPLE 5 Herbicidal Activity To evaluate their herbicidal activity, thecompounds of the invention were tested using as a representative rangeof plants: maize, Zea mays (Mz); rice, Oryza sativa (R); barnyard grass,Echinchloa crusgalli (BG); pea, Pisum sativum (P); linseed, Linumusitatissium (L); mustard, Sinapis alba (M); and sugar beet, Betavulgaris (SB).

The tests fall into two categories, pre-emergence and post-emergence.The pre-emergence tests involved spraying a liquid formulation of thecompound onto the soil in which the seeds of the plant species mentionedabove had recently been sown. The post-emergence tests involved twotypes of test, viz. soil drench and foliar spray tests. In the soildrench tests the soil in which seedling plants of the above species weregrowing, was drenched with a liquid formulation containing a compound ofthe invention, and in the foliar spray tests the Following proceduressimilar to those given in exam- 5 seedling plants were sprayed with sucha formulation.

TABLE 1 Melting Analysis, percent point,

Compound C. C H N ClZ-acetyl-kbenzyloxymethyl-4-ethyl-2-methy1-1,3-diox0lane oxime -96Calculated for... C|6H13NO4 65.5 7.9 4.8 Found 65. 8 8. 2 4. 7

2-acetyl-4benzyloxymethyl-2,4-dimethy1-1,B-dioxolane O'benzyloxime OilCalculated for. CQQHZ'INO-l 71. 5 7. 4 3. 8 Found 71.9 7.5 3.5

2acetyl-4-benzyloxy-methyl-Z,4-dimethyl-1,3-di0xolane O-rnethyloxime OilCalculated tor. CMHJQNO; 65. 5 7. 0 4. 8 Found 64. 4 7. 8 4. 3

2-acetyl-4-benzyloxymethyl-2,4-dirnethyl-1,3-dioxolaneO-cyanomethyloxime. Oil Calculated for. CHI-122N204 64.1 7.0 8.8 Found63. 7 6.9 8. 0

2-acetyl4benzyloxymethyl-2,4-dimethy1-1,3-dioxolane O-(rnethoxycarbonyl-Oil Calculated for. ClSH25N 6 .5 7.2 0

methyl) oxime. Found 61.0 7. 0 3. 8

-aoetyl-5-benzyloxy-2,5-dimethyl-1,3-dioxane oxime 146-149 Calculatedfor... C15l-Ig1N04 64.5 7. 6 5. 0 Found 64.1 7. 7 5. 3

2-benZoyl-4-benzyloxymethyl-2,4dimethyl-1,3-dioxolane oxime (isomer A)--138 Calculated for... C2oH33N04 70. 4 6. 8 4. 1 Found 70. 8 6. 9 4. 0

2-benzoyl-4-benzyloxymethyl-2,4-dimethyl-1,3-dioxolanc oxime (isomer B)85-86 Calculated for... CzoH33NO4 70.4 6. 8 4.1 Found 69. 4 6. 8 3. 8

thyl2-(4-benzyloxymethyl-2,4-dimethyl-1,3-dioxolan-2-yl)-2-hydroxyiminoace-Oil Calculated for... C17H-g3NO5 60.5 6. 9 4. 2 e Found 60. 9 6.8 4. 4

Ethyl2(4-benzyl0xymethyl-2,4dimethy]-1,3-dioxolan-2-yl)-2-methoxyiminoace-Oil Calculated for- CHHHN 06 6t. 5 7. 2 4. 0 iate- Found 62.3 7.3 3. S)Ethyl2-(4-benzyloxymethyLZA-dimethyl-l,3-dioxolan-2-yl)-l-acetoxyirninoaceOil Calculated for- C1QHQ5NO1 60. 1 6. 6 3. 7 Found 61.0 6. 8 3. 9

Ethyl2-(4-benZyloxymethyl-2,4-dimethyl-1,3-dioxolan-2-yl)-2-(N-methylcarbam-Oil Calculated for. CmHzsNaOv 57. 9 6. 6 7. 1 y y min0)acetate. Found.57. 7 6. 5 6. 7

4-benZyl0xymethyl-4-methyl-1,3-dioxolane-2-spir0(Z-hydroxyiminocyclopentane).Oil Calculated for CmH NOi 66.0 7.3 4.8 Found... 66.0 7. 2 4. 2

Ethyl2-(4benzyloxymethyl-2,4-din1ethyl-l,3-dioxolan-2-yl)-2-(N-allylcarbam-Oil Calculated for- CZIHEQNQO] 60.0 6.7 6.7 Y Y min0)acetate. I Found60. 1 6. 7 7. 0

4-benzyloxymethyl-2,4-dimethyl-2-lormyl-l,B-dioxolone O(N-methylcarbamOil Calculated for- CIBIIQ-JN205 59. 6 6. 9 8. 7

oyl)oxime. Found 09. 8 7.1 8. 4

4-benzyloxymethyl-2,4-dimethy1-2-Iormyl-1,3-dioxo]aneO-mathoxymethyloxime Oil Calculated for. CmHgsNO; 62.1 7. 5 4. 5 Found62. 2 7. 8 4. 2

4-benzyloxymethyl-2,4-dimethyl-2-formyl-1-3-formyl-1,3-dioxolaneO-(N-phen- Oil Calculated for. O2QIIf5N-305 66. 3 6. 6 7.0ylcarbamoyhnethyl)oxime. Found 65. 1 6. 6 6. 4

=l-benzyloxymethyl-2,4-dimethyl-2-(2-oxopropyl)-1,3-dioxolaneO-(N-methyl- Oil Calculated for- CraHasNzOa 61. 7 7. 4 8. 0carbamoyDoxime. Found 61. t) 7. 8 7. 6

4-benzyloxymethyl-Z,4-dimethyl-l-(Z-oxopropyl)-1.3-dioxolaneOmethyloxime... Oil Calculated for. CITE-5N0; 66. 5 8. 2 4. 6 Found 67.08. 5 4.0

v 2 75-100 Calculated for... CLEHWNOJCIQ 51.8 5.5 4. 0 20.4 ifi gylnfigodgeghchloiobenzyloxymethyl) -,4 dimethyl 1,3 dioxolanc oxime FoundL 3 5. 5 3. 9 20' 2 wA-dimethvl-4-(Q-methylbenzyloxymethyl)-1,3-dioxolane oxime (isomer OilCalculated for... CwHfltiN t 5.

i Found 65. 2 7. u 4.8

6.9 4.2 50.1 6.8 4.2 iage an PRE-HIGYRGEIE Soil. Spray HZ R m Analysis,percent Calculated fOlL CMILJQNOJ Found.

Calculated for... C21II24N4O1 Found Found Found...

Foliar Spray Melting point,

Oil

Oil Calculated for CullgsNgOa Oil Calculated for" CltlieiiNzSOg OilCalculated i011. C22I-I20N204 Oil Calculated fOl. Cg4 ll N-307 Oil148-155 Calculated I01... CQOHQQNOJ Oil Calculated for C14HwNO OilCalculated for c H NOiNa Oil Calculated for. CwH aNOq Oil Calculatedfor. C1sH21NO4 Oil Calculated for.. C1sHz1NO4 kilograms of activematerial per hectare in a volume equivalent to approximately 3,000litres per hectare.

In the pre-emergence tests untreated sown soil and in the post-emergencetests untreated soil bearing seedling plants were used as controls.

The herbicidal effects of the compounds were asdrenching the soil andeleven days after spraying the soil, and were recorded on a 09 scale. Arating 0 indicates no effect on the treated plants, a rating 2 indicatesa reduction in fresh weight of stem and leaf of the plants ofapproximately 25%, a rating 5 indicates a reduction of approximately arating 9 indicates a reduction of etc.

The results of the tests are set out in Table 2.

POST-EMERGING}! modi- 4Q sessed visually seven days after spraying thefol i R -CH-D Soil Drench TABLE 1- Continued ich half the WAGE lg/haCompound yl-2,4-dimethyl-1,3-diox0laue ZA-dinitrophenylhydrazoucmixture).

placed by vermiculite. tests were prepared by ions of the compounds byweight of an alkylphenolate available under the trade pray and foliarspray diluted with an equal g formulations applied ding to 10 and 1kiloectare respectively in a 5 per hectare. In the soil COIPOWD Clg 01!C lls. Gov-bond (isomr The soil used in the tests was a steam-sterilisedThe formulations used in the c ll Cov .bond

(Ill5 [26H Cav.bond

2-acctyl-4-benzyloxymeth amoyloxyimlno)acetate.

Ethyl2-(4-benzyloxyn1ethyl-2,4-dimethyl-1,3-dioxolan-2-yl)-2-(N-(2,4-dichlorophenyl)-carbamoyl0xyimino)acetatc.

4-benzyloxyrnethyl-4-ethyl-2-formyl-2-methyl-] ,3-dioxolane oxime4-benzyloxymethyl-2,4-dimethyl-2-formyl-1,3-dioxo1ane-o-methyloxime l2-acct-yl-2,4-dimethyl-4-(Z-methylbenZyl0xymethyl)-1.3-dioxolane oximc(isomer 2-acetyl-4-benZyloxymethyl-2,4-dimethyl-1,3-diox0lanedirnethylhydrazonc.

2-acetyl-4-beuzyloxymethyl-2,4-dimethyl-L3-dioxolane thiosemicarbazone,

2-acetyl-4-benzyloxymethyl-2,4-dimethyl-1,3-dioxolane benZoylhydraZone.

Ethyl2-(4-beuzyloxymethyl-2,4-dimethyl-1,3-dioxolau-2-yl)-2-(N-phenylcar-Z-benZoyl-5benzyloxy-2,5-dimethyl-1.3-dioxaue oxime (isomer mixture)-2-acetyl-4-benZyl0xymethyl-4-ethyl-2-rnethyl-1,3-dioxolane oxime sodiumsaltnu. Calculated for... cm mN iNa Ethyl2-(S-benzyloxy-fl,5-dimethyl-1,3-dioxan-2-yl)-2-hydroxyiminoacetate..-111 Calculated for... CnHzaN 0e4-benzyloxymethyl-2A-dimethyl-2-tormyl-1,3-dioxolane oxime.

4-benzyloxymethyI-2,4-dimethyl-Z-formyl-l,3-diox0lane oxime sodium salt.

-benZy oxymethyl-2,4-dimethyl-2-(2-oxopropyl)-1,3-dioxolane 0xime fiedJohn Innes Compost mixture in wh peat, by loose bulk, had been rediluting with water and solut acetone containing 0.4%

lethylene oxide condens name Triton X-l55. In the soil 5 tests theacetone solutions were volume of water and the resultin at two dosagelevels correspon grams of active material per h volume equivalent to 400litre drench tests one volume of the acetone solution was diluted tovolumes with water and the resulting formulation applied at one dosagelevel equivalent to 10 to 6 carbon atoms, or by N-phenylcarbamoyl,alkynyloxy or alkanoyloxy each of upto 6 carbon atoms, carbamoyloxymono-N-substituted by alkyl or alkenyl each of up to 6 carbon atoms, orby dihalophenyl, benzyloxy, amino substituted by two alkyls each of 1-6carbon atoms or by thiocarbamoyl, benzoyl or dinitrophenyl; R is benzyloptionally substituted by two chlorine atoms or by alkyl of l-6 carbonatoms; and A is a covalent bond or is methylene.

2. An oxime as defined in Formula 11, claim 1, wherein R and R each isalkyl of 1-6 carbon atoms; R is alkyl or alkoxycarbonyl each of up to 6carbon atoms, or phenyl; R is hydroxy; R is benzyl; and A is a covalentbond.

3. An oxime as defined in Formula I, claim 1, wherein R and R each is amethyl or ethyl; R is hydrogen or methyl, ethoxycarbonyl or phenyl; or Rand R together represent trimethylene; R is hydroxy or a sodium saltthereof, methoxy optionally substituted by cyano, methoxy,methoxycarbonyl or N-phenylcarbamoyl, propynyloxy or acetoxy,carbamoyloxy mono-N-substituted by methyl, ethyl, propenyl ordichlorophenyl, benzyloxy, or amino substituted by two methyls, or bythiocarbamoyl, benzoyl or dinitrophenyl; R is benzyl optionallysubstituted by two chlorines or by methyl; and A is a covalent bond oris methylene.

4. An oxime as defined in Formula II, claim 1, wherein R and R each ismethyl; R is methyl, ethoxycarbonyl or phenyl; R is hydroxy; R isbenzyl; and A is a covalent bond.

5. An oxime as defined in Formula 1, claim 1, wherein R, is methyl, R ismethyl, R is methyl, R is hydroxy and R is phenyl.

6. An oxime as defined in Formula I, claim 1, wherein R, is ethyl, R ismethyl, R is methyl, R is hydroxy and R is phenyl.

7. An oxime as defined in Formula I, claim 1, wherein R is methyl, R ismethyl, R is methyl, R is methoxy and R is phenyl.

1. AN OXIME OF ONE OF THE FOLLOWING ISOMERIC FORMULAE:
 1. An oxime ofone of the following isomeric formulae:
 2. An oxime as defined inFormula II, claim 1, wherein R1 and R2 each is alkyl of 1-6 carbonatoms; R3 is alkyl or alkoxycarbonyl each of up to 6 carbon atoms, orphenyl; R4 is hydroxy; R5 is benzyl; and A is a covalent bond.
 3. Anoxime as defined in Formula I, claim 1, wherein R1 and R2 each is amethyl or ethyl; R3 is hydrogen or methyl, ethoxycarbonyl or phenyl; orR2 and R3 together represent trimethylene; R4 is hydroxy or a sodiumsalt thereof, methoxy optionally substituted by cyano, methoxy,methoxycarbonyl or N-phenyl-carbamoyl, propynyloxy or acetoxy,carbamoyloxy mono-N-substituted by methyl, ethyl, propenyl ordichlorophenyl, benzyloxy, or amino substituted by two methyls, or bythiocarbamoyl, benzoyl or dinitrophenyl; R5 is benzyl optionallysubstituted by two chlorines or by methyl; and A is a covalent bond oris methylene.
 4. An oxime as defined in Formula II, claim 1, wherein R1and R2 each is methyl; R3 is methyl, ethoxycarbonyl or phenyl; R4 ishydroxy; R5 is benzyl; and A is a covalent bond.
 5. An oxime as definedin Formula I, claim 1, wherein R1 is methyl, R2 is methyl, R3 is methyl,R4 is hydroxy and R5 is phenyl.
 6. An oxime as defined in Formula I,claim 1, wherein R1 is ethyl, R2 is methyl, R3 is methyl, R4 is hydroxyand R5 is phenyl.